TWI798299B - Chemical and stain resistant thermoplastic polyurethane composition and method of increasing chemical and stain resistance of articles - Google Patents
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Abstract
Description
本發明係關於熱塑性聚胺甲酸酯組成物，其可被用於需要抗化學性與防沾污性以及透明性的物件中。 This invention relates to thermoplastic polyurethane compositions which can be used in articles requiring chemical and stain resistance as well as transparency.
使用熱塑性聚胺甲酸酯所製成的物件，通常需要抗化學降解和染色的性質。這對於同樣也是透明之物件或材料來說，尤其具有挑戰性。因此，需要能夠抗化學降解與染色之熱塑性聚胺甲酸酯組成物。另外，在一些實施例中，熱塑性聚胺甲酸酯組成物也需要是透明的。 Objects made from thermoplastic polyurethane generally require resistance to chemical degradation and staining. This is especially challenging for objects or materials that are also transparent. Accordingly, there is a need for thermoplastic polyurethane compositions that are resistant to chemical degradation and staining. Additionally, in some embodiments, the thermoplastic polyurethane composition also needs to be transparent.
本發明提供一種熱塑性聚胺甲酸酯組成物，其包含下列成分之反應產物(1)：一聚異氰酸酯成分，其中該聚異氰酸酯成分包括六亞甲基-1,6-二異氰酸酯；(2)一多元醇成分；以及(3)一擴鏈劑成分，其中該擴鏈劑成分包含以伸烷基取代之螺環化合物，該螺環化合物包含一以伸烷基取代的飽和螺環-二醇、一以伸烷基取代的飽 和螺環-二胺、或其等之組合，其中該以伸烷基取代的螺環化合物含有每個環具有5至7個原子之兩個環，且其中每個環係被以羥基或胺封端之含有1至4個碳原子之伸烷基所取代，其中該胺係為一級胺或二級胺。在一具體實施例中，該多元醇成分可以是一聚醚多元醇。在另一具體實施例中，該多元醇成分可以是一聚酯多元醇。 The present invention provides a thermoplastic polyurethane composition, which comprises the reaction product (1) of the following components: a polyisocyanate component, wherein the polyisocyanate component includes hexamethylene-1,6-diisocyanate; (2) a polyhydric alcohol component; and (3) a chain extender component, wherein the chain extender component comprises a spiro compound substituted with an alkylene group, and the spiro compound comprises a saturated spiro ring substituted with an alkylene group-di Alcohol, a saturated alkylene substituted A combination of a spiro-diamine, or the like, wherein the alkylene-substituted spiro compound contains two rings each having 5 to 7 atoms, and wherein each ring is replaced by a hydroxyl group or an amine A capped alkylene group containing 1 to 4 carbon atoms is substituted, wherein the amine is a primary amine or a secondary amine. In one embodiment, the polyol component may be a polyether polyol. In another embodiment, the polyol component may be a polyester polyol.
在一具體實施例中，本發明提供一種熱塑性聚胺甲酸酯組成物，其包含下列成分之反應產物：(1)一聚異氰酸酯成分，其中該聚異氰酸酯成分包含至少90莫耳%的六亞甲基-1,6-二異氰酸酯；(2)一多元醇成分；以及(3)一擴鏈劑成分，其中該擴鏈劑成分包含至少90莫耳%之以伸烷基取代的螺環化合物，該螺環化合物包含一以伸烷基取代的飽和螺環二醇、一以伸烷基取代的飽和螺環二胺、或其等之組合，其中該以伸烷基取代的螺環化合物含有每個環具有5至7個原子之兩個環，且其中每個環係被以羥基或胺封端之含有1至4個碳原子之伸烷基所取代，其中該胺係為一級胺或二級胺。在一具體實施例中，該多元醇成分可以是一聚醚多元醇。在另一具體實施例中，該多元醇成分可以是一聚酯多元醇。在另一具體實施例中，該多元醇可以選自於聚(四亞甲基醚)二醇、聚己內酯多元醇、或聚己二酸乙酯丁酯(polyethylene butylene adipate)、或其等之組合。 In a specific embodiment, the present invention provides a thermoplastic polyurethane composition comprising the reaction product of the following components: (1) a polyisocyanate component, wherein the polyisocyanate component comprises at least 90 mole percent hexaethylene Methyl-1,6-diisocyanate; (2) a polyol component; and (3) a chain extender component, wherein the chain extender component comprises at least 90 mole % of spiro rings substituted with alkylene Compound, the spiro compound comprises a saturated spiro diol substituted with an alkylene, a saturated spiro diamine substituted with an alkylene, or a combination thereof, wherein the spiro compound substituted with an alkylene Containing two rings of 5 to 7 atoms each, and wherein each ring system is substituted by an alkylene group of 1 to 4 carbon atoms terminated by a hydroxyl group or an amine, wherein the amine is a primary amine or secondary amines. In one embodiment, the polyol component may be a polyether polyol. In another embodiment, the polyol component may be a polyester polyol. In another specific embodiment, the polyol can be selected from poly(tetramethylene ether) glycol, polycaprolactone polyol, or polyethylene adipate butyl (polyethylene butylene adipate), or its etc. combination.
本發明另外提供由在此所描述之任何熱塑性聚胺甲酸酯組成物所製成之物件。 The present invention additionally provides articles made from any of the thermoplastic polyurethane compositions described herein.
本發明亦提供一種增加物件的抗化學性與防 沾污性的方法，其係藉著使用在此所描述之熱塑性聚胺甲酸酯組成物來製成該物件。明確地說，上述任何熱塑性聚胺甲酸酯組成物，均可被用於該方法中。 The invention also provides a method for increasing the chemical resistance and anti-corrosion properties of objects. A method of soiling by making the article using the thermoplastic polyurethane composition described herein. Specifically, any thermoplastic polyurethane composition described above may be used in the method.
本發明的熱塑性聚胺甲酸酯組成物(TPU)包括以下成分之反應產物(1)包含至少90莫耳%的六亞甲基-1,6-二異氰酸酯之一聚異氰酸酯成分、(2)一多元醇成分、以及(3)包含至少90莫耳%之以伸烷基取代的螺環化合物之一擴鏈劑成分，該以伸烷基取代的螺環化合物包含一以伸烷基取代的飽和螺環二醇、一以伸烷基取代的飽和螺環二胺、或其等之組合，其中該以伸烷基取代的螺環化合物含有每個環具有5至7個原子之兩個環，且其中每個環係被以羥基或胺封端之含有1至4個碳原子之伸烷基所取代，其中該胺係為一級胺或二級胺。用來聚合這些反應物以合成TPU的技術，可以採用傳統的加工設備、催化劑與製程。該聚合作用可以將會得到所欲之聚合物特性或性質之方式來進行。可以用於製備本發明之TPU的聚合技術，包括有例如反應性擠壓、批次加工、溶液聚合、與鑄塑聚合之傳統方法。 The thermoplastic polyurethane composition (TPU) of the present invention comprises a reaction product of the following components (1) comprising at least 90 mole % of a polyisocyanate component of hexamethylene-1,6-diisocyanate, (2) a polyol component, and (3) a chain extender component comprising at least 90 mole percent of an alkylene-substituted spiro compound comprising an alkylene-substituted spiro compound A saturated spirocyclic diol, a saturated spirocyclic diamine substituted with an alkylene group, or a combination thereof, wherein the alkylene-substituted spirocyclic compound contains two of 5 to 7 atoms per ring ring, and wherein each ring is substituted by an alkylene group containing 1 to 4 carbon atoms terminated by a hydroxyl group or an amine, wherein the amine is a primary amine or a secondary amine. The techniques used to polymerize these reactants to synthesize TPU can use conventional processing equipment, catalysts and processes. The polymerization can be carried out in such a way that the desired polymer characteristics or properties will be obtained. Polymerization techniques that can be used to prepare the TPU of the present invention include conventional methods such as reactive extrusion, batch processing, solution polymerization, and cast polymerization.
本發明之熱塑性聚胺甲酸酯組成物包括聚異氰酸酯成分。通常被用來製備熱塑性聚胺甲酸酯組成物之異氰酸酯，包括脂族和芳族二異氰酸酯。脂族二異氰 酸酯包括六亞甲基-1,6-二異氰酸酯(HDI)、異佛爾酮二異氰酸酯(IPDI)、1,4-環己基二異氰酸酯(CHDI)、癸烷-1,10-二異氰酸酯、離胺酸二異氰酸(LDI)、1,4-丁烷二異氰酸酯(BDI)、1,4-雙(異氰酸基甲基)環己烷(1,4-H6XDI)、以及二環己基甲烷-4,4'-二異氰酸酯(H12MDI)。芳族二異氰酸酯包括4,4'-亞甲基雙(苯基異氰酸酯)(MDI)、間二甲苯二異氰酸酯(XDI)、伸苯基-1,4-二異氰酸酯、萘-1,5-二異氰酸酯(NDI)、二苯基甲烷-3,3'-二甲氧基-4,4'-二異氰酸酯、或甲苯二異氰酸酯(TDI)。上述二異氰酸酯的二聚體與三聚體，以及兩種或更多種二異氰酸酯的摻合物，可以被用來製備熱塑性聚胺甲酸酯。 The thermoplastic polyurethane composition of the present invention includes a polyisocyanate component. Isocyanates commonly used to prepare thermoplastic polyurethane compositions include aliphatic and aromatic diisocyanates. Aliphatic diisocyanates Esters include hexamethylene-1,6-diisocyanate (HDI), isophorone diisocyanate (IPDI), 1,4-cyclohexyl diisocyanate (CHDI), decane-1,10-diisocyanate, Lysine diisocyanate (LDI), 1,4-butane diisocyanate (BDI), 1,4-bis(isocyanatomethyl)cyclohexane (1,4-H6XDI), and bicyclo Hexylmethane-4,4'-diisocyanate (H12MDI). Aromatic diisocyanates include 4,4'-methylene bis(phenyl isocyanate) (MDI), m-xylene diisocyanate (XDI), phenylene-1,4-diisocyanate, naphthalene-1,5-diisocyanate isocyanate (NDI), diphenylmethane-3,3'-dimethoxy-4,4'-diisocyanate, or toluene diisocyanate (TDI). Dimers and trimers of the above diisocyanates, as well as blends of two or more diisocyanates, can be used to prepare thermoplastic polyurethanes.
在本發明的一具體實施例中，該聚異氰酸酯成分包含六亞甲基-1,6-二異氰酸酯，並含有少於10莫耳%，或甚至少於5莫耳%之除了六亞甲基-1,6-二異氰酸酯以外的異氰酸酯。在一些具體實施例中，該聚異氰酸酯成分係實質上不含有除了六亞甲基-1,6-二異氰酸酯以外的異氰酸酯，因而使得該聚異氰酸酯成分係由六亞甲基-1,6-二異氰酸酯所構成。 In one embodiment of the present invention, the polyisocyanate component comprises hexamethylene-1,6-diisocyanate and contains less than 10 mole %, or even less than 5 mole % of hexamethylene - Isocyanates other than 1,6-diisocyanate. In some embodiments, the polyisocyanate component is substantially free of isocyanates other than hexamethylene-1,6-diisocyanate such that the polyisocyanate component is composed of hexamethylene-1,6-diisocyanate composed of isocyanates.
本發明的該熱塑性聚胺甲酸酯組成物，包含多元醇成分。該多元醇成分可以包括聚醚或聚酯多元醇。 The thermoplastic polyurethane composition of the present invention contains a polyol component. The polyol component may include polyether or polyester polyols.
在一具體實施例中，該多元醇成分包括一聚醚多元醇。聚醚多元醇通常係衍生自總共具有2至15個碳原子之二醇或多元醇，在一些具體實施例中，烷基二醇或二醇類係與包含具有2至6個碳原子之環氧烷 (alkylene oxide)的醚類反應，典型地係為環氧乙烷或環氧丙烷或其等之混合物。舉例來說，羥基官能性聚醚可以藉著首先讓丙二醇與環氧丙烷反應，接著與環氧乙烷反應來加以製備。由環氧乙烷所產生的一級羥基比二級羥基更具反應性，因此係為較佳的。可以使用的商業聚醚多元醇包括有包含環氧乙烷與乙二醇反應之聚乙二醇(PEG)；包含環氧丙烷與丙二醇反應之聚丙二醇；包含水與四氫呋喃反應之聚(四亞甲基醚)二醇，其也可以稱為經聚合的四氫呋喃，並且通常係稱為PTMEG或聚(四亞甲基醚)二醇。適當的聚醚多元醇還包括環氧烷的聚醯胺加成物，並且可包括，例如，包含乙二胺與環氧丙烷的反應產物之乙二胺加成物、包含二伸乙基三胺與環氧丙烷的反應產物之二伸乙基三胺加成物，以及類似的聚醯胺型聚醚多元醇。在本發明的一具體實施例中，該多元醇成分係為聚醚多元醇，其中該聚醚多元醇包含有、基本上係由、或者係由PTMEG所組成。 In one embodiment, the polyol component includes a polyether polyol. Polyether polyols are generally derived from diols or polyols having a total of 2 to 15 carbon atoms. In some embodiments, alkyl diols or diols are combined with rings containing 2 to 6 carbon atoms. oxane (alkylene oxide) ether reaction, typically ethylene oxide or propylene oxide or a mixture thereof. For example, hydroxy-functional polyethers can be prepared by first reacting propylene glycol with propylene oxide, followed by ethylene oxide. Primary hydroxyl groups derived from ethylene oxide are more reactive than secondary hydroxyl groups and are therefore preferred. Commercial polyether polyols that can be used include polyethylene glycol (PEG) consisting of ethylene oxide reacted with ethylene glycol; polypropylene glycol consisting of propylene oxide reacted with propylene glycol; poly(tetraethylene glycol) composed of water reacted with tetrahydrofuran methyl ether) glycol, which may also be referred to as polymerized tetrahydrofuran, and is commonly referred to as PTMEG or poly(tetramethylene ether) glycol. Suitable polyether polyols also include polyamide adducts of alkylene oxides and may include, for example, ethylenediamine adducts comprising the reaction product of ethylenediamine and propylene oxide, Diethylenetriamine adducts of the reaction products of amines and propylene oxide, and similar polyamide-type polyether polyols. In a specific embodiment of the present invention, the polyol component is polyether polyol, wherein the polyether polyol contains, consists essentially of, or consists of PTMEG.
在另一具體實施例中，該多元醇成分可以是聚酯多元醇。聚酯多元醇可以藉由(1)一種或多種二醇與一種或多種二羧酸或酸酐的酯化反應，或是(2)藉由酯交換反應，也就是一種或多種二醇與二羧酸的酯類反應來加以製備。二醇比酸通常過量1莫耳之莫耳比係為較佳的，以獲得具有較多末端羥基之直鏈結構。所需聚酯的二羧酸可以是脂族、環脂族、芳族或其等之組合。可以單獨或以混合物形式使用之適當的二羧酸，通常具有總共4至15個碳原子，並且係包括有：丁二酸、戊二酸、己 二酸、庚二酸、辛二酸、壬二酸、癸二酸、十二烷二酸、間苯二甲酸、對苯二甲酸、環己烷二羧酸、以及類似物。也可以使用上述二羧酸之酸酐，例如鄰苯二甲酸酐、四氫鄰苯二甲酸酐或類似物。己二酸係為較佳的酸。反應形成所需聚酯中間體的二醇可以是脂族、芳族或其等之組合，其包括上述擴鏈劑部分中所描述的任何二醇，並且總共具有2至20或2至12個碳原子。適當的具體例包括乙二醇、1,2-丙二醇、1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、2,2-二甲基-1,3-丙二醇、1,4-環己烷二甲醇、十亞甲基二醇、十二亞甲基二醇、以及其等之混合物。 In another specific embodiment, the polyol component can be a polyester polyol. Polyester polyols can be prepared by (1) esterification of one or more diols with one or more dicarboxylic acids or anhydrides, or (2) by transesterification, that is, one or more diols and dicarboxylic acids Acid ester reaction to be prepared. A molar ratio of usually 1 molar excess of diol to acid is preferred to obtain a linear structure with more terminal hydroxyl groups. The dicarboxylic acid of the desired polyester can be aliphatic, cycloaliphatic, aromatic or combinations thereof. Suitable dicarboxylic acids, which may be used alone or in mixtures, generally have a total of 4 to 15 carbon atoms, and include: succinic acid, glutaric acid, hexanoic acid Diacid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, and the like. Anhydrides of the aforementioned dicarboxylic acids, such as phthalic anhydride, tetrahydrophthalic anhydride or the like, may also be used. Adipic acid is a preferred acid. The diols that react to form the desired polyester intermediate can be aliphatic, aromatic, or combinations thereof, including any of the diols described in the chain extenders section above, and have a total of 2 to 20 or 2 to 12 carbon atom. Suitable specific examples include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexane Diol, 2,2-dimethyl-1,3-propanediol, 1,4-cyclohexanedimethanol, decamethylene glycol, dodecamethylene glycol, and mixtures thereof.
在一些具體實施例中，二聚脂肪酸可被用於製備聚酯多元醇，其可用於製備可用於本發明的TPU組成物。可用於製備聚酯多元醇的二聚脂肪酸之例，包括可以從Croda商業上取得的PriplastTM聚酯二醇/多元醇，以及可以從Oleon商業上取得的Radia®聚酯二醇。 In some embodiments, dimerized fatty acids can be used to prepare polyester polyols, which can be used to prepare TPU compositions useful in the present invention. Examples of dimerized fatty acids that can be used to prepare polyester polyols include Priplast ™ polyester diols/polyols commercially available from Croda, and Radia® polyester diols commercially available from Oleon.
該TPU組成物的多元醇成分，還可包含一種或多種聚己內酯聚酯多元醇。可用於在此所描述之技術中的聚己內酯聚酯多元醇，包括衍生自己內酯單體的聚酯二醇。該聚己內酯聚酯多元醇係由一級羥基來封端。適當的聚己內酯聚酯多元醇，可以由ε-己內酯與例如二乙二醇、1,4-丁二醇、單乙二醇、1,6-己二醇、2,2-二甲基-1,3-丙二醇、或其等之任何組合，或是習於此藝者已知的任何二醇以及/或是二醇之雙官能基起始劑所製成。在一些具體實施例中，該聚己內酯聚酯多元醇係為 衍生自己內酯單體的線性聚酯二醇。商業上可取得之聚己內酯多元醇之例，包括CAPATM 2202A，一種2,000數量平均分子量(Mn)之線性聚酯二醇；以及CAPATM 2302A，一種3,000Mn之線性聚酯二醇，兩者均可以從Perstorp Polyols Inc.商商業上取得。這些材料也可以被描述為2-氧環庚酮與1,4-丁二醇的聚合物。 The polyol component of the TPU composition may also contain one or more polycaprolactone polyester polyols. Polycaprolactone polyester polyols useful in the art described herein include polyester diols derived from caprolactone monomers. The polycaprolactone polyester polyol is terminated by a primary hydroxyl group. Suitable polycaprolactone polyester polyols can be formed from ε-caprolactone with, for example, diethylene glycol, 1,4-butanediol, monoethylene glycol, 1,6-hexanediol, 2,2- Dimethyl-1,3-propanediol, or any combination thereof, or any diol and/or difunctional diol starter known to those skilled in the art. In some embodiments, the polycaprolactone polyester polyol is a linear polyester diol derived from a caprolactone monomer. Examples of commercially available polycaprolactone polyols include CAPA ™ 2202A, a linear polyester diol of 2,000 number average molecular weight (Mn); and CAPA ™ 2302A, a linear polyester diol of 3,000 Mn, two Both are commercially available from Perstorp Polyols Inc. These materials can also be described as polymers of 2-oxepanone and 1,4-butanediol.
在本發明的一具體實施例中，該多元醇成分係為聚酯多元醇，其包含、基本上由、或係由聚己內酯多元醇所組成。在本發明的另一具體實施例中，該多元醇成分係為聚酯多元醇，其包含、基本上由、或係由聚己二酸乙酯丁酯(polyethylene butylene adipate)所組成。 In a specific embodiment of the present invention, the polyol component is polyester polyol, which comprises, consists essentially of, or consists of polycaprolactone polyol. In another embodiment of the present invention, the polyol component is polyester polyol, which comprises, consists essentially of, or consists of polyethylene butyl adipate (polyethylene butylene adipate).
在一些具體實施例中，該多元醇成分可以是如上該之聚醚或聚酯，但是也可以包含共聚聚醚多元醇或聚醚多元醇以及/或是共聚聚醚多元醇的混合物。在一具體實施例中，該共聚聚醚多元醇係為聚醚多元醇和一多元醇的共聚物，該多元醇係選自於聚酯多元醇、聚碳酸酯多元醇、聚己內酯多元醇或聚醯胺多元醇。 In some embodiments, the polyol component may be a polyether or a polyester as described above, but may also comprise a copolyether polyol or a mixture of polyether polyols and/or a mixture of copolyether polyols. In a specific embodiment, the copolyether polyol is a copolymer of polyether polyol and a polyol, and the polyol is selected from polyester polyol, polycarbonate polyol, polycaprolactone polyol alcohol or polyamide polyol.
本發明的擴鏈劑成分包含一以伸烷基取代的螺環化合物，其包含一以伸烷基取代的飽和螺環二醇、一以伸烷基取代的飽和螺環二胺、或是其等之組合，並且每個環均以含有1至4個碳原子之由羥基或胺封端的伸烷基來取代，其中該胺係為一級胺或二級胺。在一具體實施例中，該以伸烷基取代的螺環化合物，係為在每個環中含有2個雜原子的螺雜環，並且該雜原子係為 氧、氮、硫或磷。在一具體實施例中，該以伸烷基取代的螺環化合物，係為在每個環中含有2個雜原子的螺雜環，並且該雜原子係為氧或氮。在一具體實施例中，該以伸烷基取代的螺環化合物，係為在每個環中含有2個雜原子的螺雜環，並且該雜原子係為氧。 The chain extender component of the present invention comprises a spiro compound substituted with an alkylene group, which comprises a saturated spirocyclic diol substituted with an alkylene group, a saturated spirocyclic diamine substituted with an alkylene group, or its etc., and each ring is substituted with a hydroxyl or amine-terminated alkylene group containing 1 to 4 carbon atoms, wherein the amine is a primary amine or a secondary amine. In a specific embodiment, the spirocyclic compound substituted with alkylene is a spiroheterocyclic ring containing 2 heteroatoms in each ring, and the heteroatoms are Oxygen, nitrogen, sulfur or phosphorus. In a specific embodiment, the alkylene-substituted spirocyclic compound is a spiroheterocyclic ring containing 2 heteroatoms in each ring, and the heteroatoms are oxygen or nitrogen. In one embodiment, the alkylene-substituted spirocyclic compound is a spiroheterocyclic ring containing 2 heteroatoms in each ring, and the heteroatoms are oxygen.
在一具體實施例中，該以伸烷基取代的螺環化合物係具有以下結構式：
其中每個X係獨立地選自於O、CHR2、NR2、S、PR2，其中每個R2代表氫原子或含有1至大約6個碳原子的烷基，每個R1是含有1至4個碳原子的伸烷基，其可以是直鏈或支鏈的；每個Z係選自於-OH或-NHR3，其中R3代表氫原子或含有1至大約6個碳原子的烷基；其中a、b、c、d、e、f、g和h係各自獨立地為0至2的整數，只要a、b、c和d的總和係為1至3，並且e、f、g和h的總和係為1至3。在一具體實施例中，a等於g，b等於h，c等於e，d等於f。在一具體實施例中，所有X都是相同的。在一具體實施例中，所有X均係相同地選自O或NR2，其中R2代表氫原子或含有1至大約6個碳原子的烷基，a等於g，b等於h，c等於e和d等於f。在一具體實施例中，該螺環-二伸烷基化合物係含有兩個6-元環，X係獨立地選自於O或NR2，其中R2代表氫原 子或含有1至大約6個碳原子的烷基，R1係為含有1至4個碳原子的伸烷基，Z係為-OH或NH2，並且(i)a為0，b為1，c為1，d為0，e為1，f為0，g為0，且h為1，或者(ii)a為1，b為0，c為0，d是1，e為0，f為1，g為1，且h為0。在一具體實施例中，該螺環-二伸烷基化合物含有兩個6-元環，X係相同地選自於O或NR2，其中R2代表氫原子或含有1至大約6個碳原子的烷基，R1係為含有1至4個碳原子的伸烷基，Z係為-OH或NH2，並且(i)a為0，b為1，c為1，d為0，e為1，f為0，g為0，h為1，或(ii)a為1，b為0，c為0，d是1，e為0，f為1，g為1，h為0。在一具體實施例中，該螺環-二伸烷基化合物含有兩個6-元環，X是O，R1是1,1-二甲基乙基，Z為-OH，及(i)a為0，b為1，c為1，d為0，e為1，f為0，g為0，且h為1，或(ii)a為1，b為0，c為0，d為1，e為0，f為1，g為1，且h為0。 wherein each X is independently selected from O, CHR 2 , NR 2 , S, PR 2 , wherein each R 2 represents a hydrogen atom or an alkyl group containing 1 to about 6 carbon atoms, and each R 1 is an alkyl group containing An alkylene group of 1 to 4 carbon atoms, which may be straight or branched; each Z is selected from -OH or -NHR 3 , wherein R 3 represents a hydrogen atom or contains 1 to about 6 carbon atoms wherein a, b, c, d, e, f, g and h are each independently an integer from 0 to 2, as long as the sum of a, b, c and d is 1 to 3, and e, The sum of f, g and h is 1 to 3. In a specific embodiment, a is equal to g, b is equal to h, c is equal to e, and d is equal to f. In a specific embodiment, all X's are the same. In a specific embodiment, all X are identically selected from O or NR 2 , wherein R 2 represents a hydrogen atom or an alkyl group containing 1 to about 6 carbon atoms, a equals g, b equals h, c equals e and d is equal to f. In a specific embodiment, the spiro-dialkylene compound contains two 6-membered rings, and X is independently selected from O or NR 2 , wherein R 2 represents a hydrogen atom or contains 1 to about 6 An alkyl group of carbon atoms, R 1 is an alkylene group containing 1 to 4 carbon atoms, Z is -OH or NH 2 , and (i) a is 0, b is 1, c is 1, and d is 0 , e is 1, f is 0, g is 0, and h is 1, or (ii) a is 1, b is 0, c is 0, d is 1, e is 0, f is 1, g is 1, And h is 0. In a specific embodiment, the spiro-dialkylene compound contains two 6-membered rings, and X is identically selected from O or NR 2 , wherein R 2 represents a hydrogen atom or contains 1 to about 6 carbons Atomic alkyl, R 1 is an alkylene group containing 1 to 4 carbon atoms, Z is -OH or NH 2 , and (i) a is 0, b is 1, c is 1, d is 0, e is 1, f is 0, g is 0, h is 1, or (ii) a is 1, b is 0, c is 0, d is 1, e is 0, f is 1, g is 1, h is 0. In one embodiment, the spiro-dialkylene compound contains two 6-membered rings, X is O, R is 1,1 -dimethylethyl, Z is -OH, and (i) a is 0, b is 1, c is 1, d is 0, e is 1, f is 0, g is 0, and h is 1, or (ii) a is 1, b is 0, c is 0, d is 1, e is 0, f is 1, g is 1, and h is 0.
在一具體實施例中，該以伸烷基取代的螺環化合物係呈現微以下之結構式：
其中每個X均係獨立地選自於O、CHR2、NR2、S、PR2，其中每個R2代表氫原子或含有1至大約6個碳原子的烷基，每個R1均係為含有1至4個碳原子的伸烷基，其可以是直鏈或支鏈的；並且每個Z係選自於-OH 或-NHR3，其中R3代表氫原子或含有1至大約6個碳原子的烷基。在一具體實施例中，X係相同地選自於O、CHR2、NR2、S、PR2，其中每個R2代表氫原子或含有1至大約6個碳原子的烷基。在一具體實施例中，X係為O，R1係為1,1-二甲基乙基，且Z係為-OH。 wherein each X is independently selected from O, CHR 2 , NR 2 , S, PR 2 , wherein each R 2 represents a hydrogen atom or an alkyl group containing 1 to about 6 carbon atoms, and each R 1 is The system is an alkylene group containing 1 to 4 carbon atoms, which may be straight or branched; and each Z system is selected from -OH or -NHR 3 , wherein R 3 represents a hydrogen atom or contains 1 to about An alkyl group of 6 carbon atoms. In a specific embodiment, X is identically selected from O, CHR 2 , NR 2 , S, PR 2 , wherein each R 2 represents a hydrogen atom or an alkyl group containing 1 to about 6 carbon atoms. In one embodiment, X is O, R is 1,1 -dimethylethyl, and Z is -OH.
在一具體實施例中，擴鏈劑成分包含如在此所描述之一以伸烷基取代的螺環化合物，並且除了以伸烷基取代的螺環化合物之外，含有小於10莫耳%之一共擴鏈劑。共擴鏈劑可以包括脂族或脂環族二胺或二醇，其具有2至20、或2至12、或2至10個碳原子，或是其等之組合。共擴鏈劑之例包括乙二醇、二乙二醇、丙二醇、二丙二醇、1,3-丙二醇、1,4-丁二醇(BDO)、1,6-己二醇(HDO)、1,3-丁二醇、1,5-戊二醇、新戊二醇、1,4-環己烷二甲醇(CHDM)、六亞甲基二醇、庚二醇、壬二醇、十二烷二醇、2-乙基-1,3-己二醇、2,2,4-三甲基戊烷-1,3-二醇、1,4-環己烷二羥甲基、3-甲基-1,5-戊二醇、乙二胺、丁二胺、六亞甲基二胺、2-丁基-2-乙基-1,3-丙二醇等、以及其等之混合物。在一具體實施例中，該擴鏈劑成分係實質上除了以伸烷基取代的螺環化合物之外不含有共擴鏈劑，使得該擴鏈劑成分係由以伸烷基取代的螺環化合物所組成。 In a specific embodiment, the chain extender component comprises an alkylene-substituted spiro compound as described herein and, in addition to the alkylene-substituted spiro compound, contains less than 10 mole % of A total of chain extenders. Co-chain extenders may include aliphatic or cycloaliphatic diamines or diols having 2 to 20, or 2 to 12, or 2 to 10 carbon atoms, or combinations thereof. Examples of co-chain extenders include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,4-butanediol (BDO), 1,6-hexanediol (HDO), 1 ,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,4-cyclohexanedimethanol (CHDM), hexamethylene glycol, heptanediol, nonanediol, dodecane Alkanediol, 2-ethyl-1,3-hexanediol, 2,2,4-trimethylpentane-1,3-diol, 1,4-cyclohexanedimethylol, 3- Methyl-1,5-pentanediol, ethylenediamine, butylenediamine, hexamethylenediamine, 2-butyl-2-ethyl-1,3-propanediol, etc., and mixtures thereof. In one embodiment, the chain extender component is substantially free of co-chain extenders other than the alkylene substituted spiro compound such that the chain extender component is composed of alkylene substituted spiro compounds. composed of compounds.
TPU組成物的該異氰酸酯成分與該擴鏈劑成分，通常被稱為TPU的「硬質區塊」。在本發明的一具體實施例中，該TPU組成物含有大於50重量%，或甚至為至少55重量%，或甚至至少60重量%的硬質區塊。根 據本發明製成的TPU組成物，可以具有40D至85D之蕭氏D硬度(Shore D hardness)，例如50D至80D。在一具體實施例中，該TPU包含以下成分之反應產物：25重量%至30重量%之聚異氰酸酯成分，其係包含、基本上由或係由六亞甲基-1,6-二異氰酸酯所組成；20重量%至40重量%之聚醚多元醇；以及30重量%至45重量%之擴鏈劑成分，該擴鏈劑成分係包含、基本上由或係由以伸烷基取代的螺環化合物所組成，該伸烷基取代的螺環化合物包含以伸烷基取代的飽和螺環二醇、以伸烷基取代的飽和螺環二胺、或其等之組合。 The isocyanate component and the chain extender component of the TPU composition are generally referred to as the "hard block" of TPU. In a specific embodiment of the present invention, the TPU composition contains more than 50% by weight, or even at least 55% by weight, or even at least 60% by weight of hard blocks. root The TPU composition made according to the present invention may have a Shore D hardness of 40D to 85D, for example, 50D to 80D. In one embodiment, the TPU comprises the reaction product of 25% to 30% by weight of a polyisocyanate component comprising, consisting essentially of, or consisting of hexamethylene-1,6-diisocyanate Composition; 20% by weight to 40% by weight of polyether polyol; and 30% by weight to 45% by weight of a chain extender component comprising, consisting essentially of, or consisting of, an alkylene-substituted spiro The alkylene-substituted spirocyclic compound comprises a saturated spirocyclic diol substituted with an alkylene group, a saturated spirocyclic diamine substituted with an alkylene group, or a combination thereof.
在一具體實施例中，本發明提供一種熱塑性聚胺甲酸酯組成物，其包含下列成分之反應產物：(1)一聚異氰酸酯成分，其中該聚異氰酸酯成分包含至少90莫耳%的六亞甲基-1,6-二異氰酸酯；(2)一多元醇成分；以及(3)一擴鏈劑成分，其中該擴鏈劑成分包含至少90莫耳%的一以伸烷基取代的螺環化合物，該螺環化合物包含一以伸烷基取代的飽和螺環二醇、一以伸烷基取代的飽和螺環二胺、或其等之組合，其中該以伸烷基取代的螺環化合物，包含兩個每個環含有5到7個原子的環，且其中每個環係以含有1至4個碳原子之以羥基或胺封端的伸烷基來取代，其中該胺係為一級胺或二級胺。在一具體實施例中，該多元醇成分可以是聚醚多元醇。在另一具體實施例中，該多元醇成分可以是聚酯多元醇。在又另一具體實施例中，該多元醇可以選自於聚(四亞甲基醚)二醇、聚己內酯多元醇、或聚己二酸乙酯丁酯，或 其等之組合。 In a specific embodiment, the present invention provides a thermoplastic polyurethane composition comprising the reaction product of the following components: (1) a polyisocyanate component, wherein the polyisocyanate component comprises at least 90 mole percent hexaethylene Methyl-1,6-diisocyanate; (2) a polyol component; and (3) a chain extender component, wherein the chain extender component comprises at least 90 mole % of an alkylene substituted spiro Cyclic compound, the spiro compound comprises a saturated spiro diol substituted with an alkylene, a saturated spirodiamine substituted with an alkylene, or a combination thereof, wherein the spirocyclic substituted with an alkylene Compounds comprising two rings each containing 5 to 7 atoms, and wherein each ring is substituted with a hydroxyl or amine-terminated alkylene group containing 1 to 4 carbon atoms, wherein the amine is a primary Amines or secondary amines. In a specific embodiment, the polyol component may be a polyether polyol. In another specific embodiment, the polyol component can be a polyester polyol. In yet another specific embodiment, the polyol may be selected from poly(tetramethylene ether) glycol, polycaprolactone polyol, or polyethylene butyl adipate, or combinations thereof.
在一具體實施例中，本發明提供一種熱塑性聚胺甲酸酯組成物，其包含下列成分之反應產物：(1)一聚異氰酸酯成分，其中該聚異氰酸酯成分係由六亞甲基-1,6-二異氰酸酯所組成；(2)一多元醇成分；以及(3)一擴鏈劑成分，其中該擴鏈劑成分係由以伸烷基取代的螺環化合物所組成，該螺環化合物包含一以伸烷基取代的飽和螺環二醇、一以伸烷基取代的飽和螺環二胺、或其等之組合，其中該以伸烷基取代的螺環化合物，含有兩個每個環含有5到7個原子的環，且其中每個環係以含有1至4個碳原子之以羥基或胺封端的伸烷基來取代，其中該胺係為一級胺或二級胺，並且其中該擴鏈劑成分除了該以伸烷基取代的螺環化合物之外，含有少於10莫耳%共擴鏈。在此一具體實施例中，該多元醇成分可以包含、基本上由、或係由聚(四亞甲基醚)二醇、聚己內酯多元醇、或聚己二酸乙酯丁酯、或其等之組合所組成。 In a specific embodiment, the present invention provides a thermoplastic polyurethane composition, which comprises the reaction product of the following components: (1) a polyisocyanate component, wherein the polyisocyanate component is composed of hexamethylene-1, (2) a polyol component; and (3) a chain extender component, wherein the chain extender component is composed of a spiro compound substituted with an alkylene group, the spiro compound Comprising a saturated spirocyclic diol substituted with an alkylene group, a saturated spirocyclic diamine substituted with an alkylene group, or a combination thereof, wherein the spirocyclic compound substituted with an alkylene group contains two each The ring contains 5 to 7 atoms, and wherein each ring system is substituted with a hydroxyl or amine-terminated alkylene group containing 1 to 4 carbon atoms, wherein the amine is a primary amine or a secondary amine, and Wherein the chain extender component contains less than 10 mole % of co-extended chain except for the spiro compound substituted with alkylene. In one embodiment, the polyol component may comprise, consist essentially of, or consist of poly(tetramethylene ether) glycol, polycaprolactone polyol, or polyethylene butyl adipate, or a combination thereof.
在一具體實施例中，本發明的TPU組成物藉著呈現出小於35或甚至小於31，或是17或甚至更小的△E，而顯現出對於依據ASTM D6578M-13之永久性標記染色的抵抗性。在一具體實施例中，該TPU組成物係為透明，也就是，依據ASTM D1003-11來進行測量，其具有小於20或15或更小之霧狀程度。在一具體實施例中，本發明的TPU組成物還呈現出依據EN 438-2，係為至少4.5，或甚至為5(目視評斷)之平均抗化學性。 In one embodiment, the TPU composition of the present invention exhibits resistance to permanent marker staining according to ASTM D6578M-13 by exhibiting a ΔE of less than 35, or even less than 31, or 17 or even less. resistance. In one embodiment, the TPU composition is transparent, ie, has a haze of less than 20 or 15 or less as measured according to ASTM D1003-11. In one embodiment, the TPU composition of the invention also exhibits an average chemical resistance according to EN 438-2 of at least 4.5, or even 5 (visual evaluation).
另一方面，本發明進一步揭露了一種製備在 此所描述之該TPU組成物的方法，其包含將(1)包含六亞甲基-1,6-二異氰酸酯的一聚異氰酸酯成分、(2)一多元醇成分、以及(3)一擴鏈劑成分來進行反應，其中該擴鏈劑成分包含一以伸烷基取代的螺環化合物，該螺環化合物包含一以伸烷基取代的飽和螺環二醇、一以伸烷基取代的飽和螺環二胺、或其等之組合，其中該以伸烷基取代的螺環化合物，包含兩個每個環含有5到7個原子的環，且其中每個環係以含有1至4個碳原子之以羥基或胺封端之伸烷基來取代，其中該胺係為一級胺或二級胺；可以得到抗化學性降解與玷污之一TPU組成物。該TPU組成物的成分應被理解為包括在此之各種具體實施例中所描述的所有元素。 On the other hand, the present invention further discloses a preparation in The method for the TPU composition described herein comprises combining (1) a polyisocyanate component comprising hexamethylene-1,6-diisocyanate, (2) a polyol component, and (3) a polyisocyanate component The chain agent component is used to react, wherein the chain extender component comprises a spiro compound substituted with an alkylene group, and the spiro compound comprises a saturated spirocyclic diol substituted with an alkylene group, an alkylene substituted A saturated spirocyclic diamine, or a combination thereof, wherein the spirocyclic compound substituted with an alkylene group comprises two rings each containing 5 to 7 atoms, and wherein each ring contains 1 to 4 A carbon atom is replaced by a hydroxyl group or an amine-terminated alkylene group, wherein the amine is a primary amine or a secondary amine; a TPU composition that is resistant to chemical degradation and staining can be obtained. The composition of the TPU composition should be understood to include all the elements described in the various embodiments herein.
製備本發明的TPU聚合物之方法，可以使用傳統的以及在此之後開發的TPU製造設備，以及已知的或是在此之後開發的方法。該等三種反應物(該異氰酸酯成分、該聚醚多元醇、與該擴鏈劑成分)係被反應，以形成可用於本發明的TPU。 The method for preparing the TPU polymer of the present invention can use conventional and hereafter developed TPU manufacturing equipment, as well as known or hereafter developed methods. The three reactants (the isocyanate component, the polyether polyol, and the chain extender component) are reacted to form a TPU useful in the present invention.
在一具體實施例中，該方法係為所謂的「單次(one-shot)」製程，其中所有的三種反應物係被加入至擠出機反應器並進行反應。該二異氰酸酯的當量重量含量，相對於該含羥基成分的總當量重量含量(也就是該聚醚多元醇中間體與該擴鏈劑成分)，可以是從大約0.95至大約1.10，或從大約0.96至大約1.03，甚至為從大約0.97到大約1.05。在一些具體實施例中，可以任選地在該反應中使用胺基甲酸乙酯催化劑。 In one embodiment, the method is a so-called "one-shot" process, in which all three reactants are added to the extruder reactor and reacted. The equivalent weight content of the diisocyanate can be from about 0.95 to about 1.10, or from about 0.96 to about 1.03, and even from about 0.97 to about 1.05. In some embodiments, a urethane catalyst can optionally be used in this reaction.
本發明的TPU也可以利用預聚物製程來加以製備。在預聚物途徑中，多元醇中間體通常係與當量過量的一種或多種二異氰酸酯反應，以形成其中含有游離或未反應的二異氰酸酯之一預聚物溶液。在一些具體實施例中，可以任選地在該反應中使用胺基甲酸乙酯催化劑。接著，加入通常與異氰酸酯末端基團，以及與任何游離或未反應的二異氰酸酯化合物，相等當量之如上所述的擴鏈劑。因此該總二異氰酸酯，以及該多元醇中間體與該擴鏈劑的總當量之整體當量比，係為從大約0.95至大約1.10，或是從大約0.96至大約1.03，且甚至為從大約0.97至大約1.05。該鏈延長反應溫度通常係為大約100℃至大約250℃，或大約200℃至大約250℃。典型地，該預聚物途徑可以在包括擠出機之任何傳統裝置中進行。在此種具體實施例中，該多元醇中間體係在該擠出機的第一部分中，與一當量過量的二異氰酸酯反應以形成一預聚物溶液，接著該擠出機在下游部分加入一擴鏈劑，並與該預聚物溶液反應。任何傳統的擠出機都可以使用，包括配備有長度直徑比為至少20之阻障螺桿的擠出機，在一些具體實施例中係為至少25者。 The TPU of the present invention can also be prepared using a prepolymer process. In the prepolymer route, the polyol intermediate is generally reacted with an equivalent excess of one or more diisocyanates to form a prepolymer solution containing free or unreacted diisocyanate therein. In some embodiments, a urethane catalyst can optionally be used in this reaction. Next, an equivalent of the chain extender as described above, usually equivalent to the isocyanate end groups, and to any free or unreacted diisocyanate compound, is added. Thus the overall equivalent ratio of the total diisocyanate, and the total equivalents of the polyol intermediate to the chain extender, is from about 0.95 to about 1.10, or from about 0.96 to about 1.03, and even from about 0.97 to About 1.05. The chain extension reaction temperature is generally from about 100°C to about 250°C, or from about 200°C to about 250°C. Typically, the prepolymer route can be carried out in any conventional apparatus including extruders. In such embodiments, the polyol intermediate is reacted with an equivalent excess of diisocyanate in a first section of the extruder to form a prepolymer solution, followed by the addition of an extruder in a downstream section of the extruder. chain agent and react with the prepolymer solution. Any conventional extruder can be used, including extruders equipped with barrier screws having a length-to-diameter ratio of at least 20, and in some embodiments at least 25.
在一具體實施例中，將包含六亞甲基-1,6-二異氰酸酯的該聚異氰酸酯成分、該多元醇成分、以及包含以伸烷基取代的一螺環化合物之該擴鏈劑成分，在具有多個加熱區與多個進料口之單螺桿或雙螺桿擠出機上，於其之進料端以及其之模具端之間進行混合。該等成分可以在一個或多個該個進料口進行添加，並且可以 將離開該擠出機之模具端之所得到的TPU組成物進行造粒。 In a specific embodiment, the polyisocyanate component comprising hexamethylene-1,6-diisocyanate, the polyol component, and the chain extender component comprising a spiro compound substituted with alkylene, Mixing takes place between the feed end of the extruder and the die end thereof on a single or twin screw extruder with multiple heating zones and multiple feed ports. The ingredients may be added at one or more of the feed ports and may The resulting TPU composition exiting the die end of the extruder is pelletized.
在另一具體實施例中，如在此所揭露的包含六亞甲基-1,6-二異氰酸酯的該聚異氰酸酯成分、該多元醇成分、以及包含以伸烷基取代的一螺環化合物之該擴鏈劑成分，係通常被添加在一起，並依據如在此所描述之標準聚胺甲酸酯合成方法來進行反應。本發明的TPU形成成分可以在例如被稱為班布里混合機的密閉式混合器之適當混合器中，或是在擠出機中熔融聚合。在一態樣中，適當的加工或聚合溫度係為大約100℃至大約250℃，在另一態樣中則為大約200℃至大約250℃。 In another embodiment, the polyisocyanate component comprising hexamethylene-1,6-diisocyanate, the polyol component, and the polyol component comprising a spiro compound substituted with alkylene as disclosed herein The chain extender component is typically added together and reacted according to standard polyurethane synthesis methods as described herein. The TPU forming ingredients of the present invention can be melt polymerized in a suitable mixer such as an internal mixer known as a Banbury mixer, or in an extruder. In one aspect, suitable processing or polymerization temperatures are from about 100°C to about 250°C, and in another aspect from about 200°C to about 250°C.
任擇地，其也可能需要使用例如含錫的和其他金屬羧酸鹽以及三級胺之催化劑。特別是加速該二異氰酸酯的NCO基團，以及該多元醇與擴鏈劑的羥基之間的反應之適當催化劑之例，係為先前技術中已知的傳統三級胺，例如三乙胺、二甲基環己胺、N-甲基
本發明的TPU聚合物可以與本技術領域中 已知，或是在此之後開發的各種傳統添加劑或複合劑，例如抗氧化劑、殺生物劑、殺真菌劑、抗微生物劑、抗靜電添加劑、增塑劑、填料、增效劑、阻燃劑、耐衝擊性改良劑、顏料、潤滑劑、脫模劑、流變改性劑、UV吸收劑、與類似物混合。如同習於複合TPU之技藝者所已知的，傳統添加劑的含量係取決於所欲最終應用之最後性質與成本。這些額外的添加劑可以摻入TPU成分或反應混合物中，或者在製備TPU之後摻入。在另一種製程中，所有材料可以與TPU混合然後熔化，或者其等也可以直接摻入TPU組成物的熔體內。 The TPU polymer of the present invention can be with those in this technical field Various traditional additives or compounding agents known or developed hereafter, such as antioxidants, biocides, fungicides, antimicrobials, antistatic additives, plasticizers, fillers, synergists, flame retardants , impact modifiers, pigments, lubricants, release agents, rheology modifiers, UV absorbers, mixed with the like. As is known to those skilled in compounding TPU, the level of conventional additives depends on the final properties and cost of the intended end application. These additional additives can be incorporated into the TPU ingredients or reaction mixture, or after the TPU is prepared. In another process, all materials can be mixed with TPU and then melted, or they can be directly incorporated into the melt of TPU composition.
在另一態樣中，本發明係為包含在此所詳細描述之本發明的TPU之物件。包含本發明的TPU之物件可以是任何模塑物件，例如注射模塑物件。在一具體實施例中，此種TPU可被用來製造需要具有透明外層的物件。在又其他具體實施例中，含有上述各種組成物之物件，包括在使用過程中可能會暴露於化學品或染色劑(例如油墨)中之任何物件，特別是過去因為這些材料對化學降解或玷污的抵抗力不足，而未採用熱塑性聚胺甲酸酯來製成之物件。此一組成物所可以運用之物件與應用包括有，但不限於保護膜、裝飾膜、彩繪膜、標籤、地板、多層膜結構、消費性產品、電子產品、纖維複合材料、或保護性或裝飾性塗層(例如清漆)替代品。各式各樣的具體應用都可以運用本發明的TPU組成物之優點，並且僅舉例來說，包括油漆保護膜、用於內部和外部用途之玻璃保護膜、手提箱保護膜、鏡片保護膜、在號誌或其 他表面上之防塗鴉保護層、地板上的耐磨層、包括有內部和外部表面之汽車部件、電子設備的保護蓋、螢幕保護層、以及用於汽車、航太、風能與壓力容器應用之纖維複合材料上。事實上，本發明的TPU組成物可被用於習於此藝者現在已知，或後來所發現之需要具有防沾污性的透明熱塑性材料的任何應用中。 In another aspect, the invention is an article comprising the TPU of the invention as described in detail herein. The article comprising the TPU of the present invention may be any molded article, such as an injection molded article. In one embodiment, such a TPU can be used to manufacture objects that require a transparent outer layer. In yet other embodiments, articles comprising the various compositions described above include any article that may be exposed to chemicals or stains (such as inks) during use, especially in the past due to the resistance of these materials to chemical degradation or staining. Insufficient resistance and not made of thermoplastic polyurethane. Objects and applications for which this composition can be used include, but are not limited to, protective films, decorative films, painted films, labels, flooring, multilayer film structures, consumer products, electronics, fiber composites, or protective or decorative alternatives to permanent coatings such as varnishes. A wide variety of specific applications can take advantage of the advantages of the TPU composition of the present invention, and include, by way of example only, paint protection films, glass protection films for interior and exterior use, suitcase protection films, lens protection films, in the sign or Anti-graffiti protective coatings on other surfaces, wear-resistant coatings on floors, automotive components including interior and exterior surfaces, protective covers for electronic equipment, screen protectors, and for automotive, aerospace, wind energy and pressure vessel applications on fiber composite materials. In fact, the TPU composition of the present invention can be used in any application now known to those skilled in the art, or later discovered, that requires a transparent thermoplastic material with stain resistance.
本發明的組合物或其之任何摻合物，可被在任何模塑製程中用於製備本發明的模塑產品。該等模塑製成係為習於此藝者所熟知的，其包括但不限於鑄型、冷成型對模塑、壓縮成型、發泡成型、射出成型、氣體輔助射出成型、外形共擠出、外形擠出、旋轉鑄型、片材擠出、中空鑄型、噴塗技術、熱成型、轉注成型、真空成型、濕敷或接觸模製、吹塑、擠壓吹塑、射出吹塑和注拉吹塑或其等之組合。 The compositions of the present invention, or any blends thereof, may be used in any molding process to prepare molded products of the present invention. Such moldings are well known to those skilled in the art and include, but are not limited to, casting, cold forming, compression molding, foam molding, injection molding, gas assisted injection molding, profile coextrusion , shape extrusion, rotational casting, sheet extrusion, hollow casting, spray technology, thermoforming, transfer molding, vacuum forming, wet lay or contact molding, blow molding, extrusion blow molding, injection blow molding and injection Stretch blow molding or a combination thereof.
在另一個態樣中，本發明係與一種係藉著製造包含有效量之熱塑性聚胺甲酸酯(TPU)的物件，來增加一物件之抗化學物與玷污的方法有關，其中該TPU包含下列成分之反應產物：(1)一脂族聚異氰酸酯，其包含、或基本上由、或係由六亞甲基-1,6-二異氰酸酯所組成；(2)如在此所描述之一多元醇成分；以及(3)擴鏈劑成分，其包含、或基本上由、或係由以伸烷基取代之螺環化合物所組成，該螺環化合物包含以伸烷基取代的飽和螺環二醇、以伸烷基取代的飽和螺環-二胺、或其等之組合，其中該以伸烷基取代的螺環化合物，含有每個環具有5到7個原子的兩個環，且其中每個環被含有1至4個碳 原子以羥基或胺封端的伸烷基所取代，其中該胺係為一級胺或二級胺。 In another aspect, the invention relates to a method of increasing the chemical and stain resistance of an article by making the article comprising an effective amount of thermoplastic polyurethane (TPU), wherein the TPU comprises The reaction product of: (1) an aliphatic polyisocyanate comprising, consisting essentially of, or consisting of hexamethylene-1,6-diisocyanate; (2) one of the A polyol component; and (3) a chain extender component comprising, or consisting essentially of, or consisting of, a spiro compound substituted with an alkylene group, the spiro compound comprising a saturated spiro compound substituted with an alkylene group Cyclic diols, saturated spiro-diamines substituted with alkylene groups, or combinations thereof, wherein the spirocyclic compounds substituted with alkylene groups contain two rings each having 5 to 7 atoms, and each ring is composed of 1 to 4 carbons Atoms are substituted with hydroxyl or amine-terminated alkylene, where the amine is a primary or secondary amine.
本發明的技術還包括一熱塑性聚胺甲酸酯組成物的用途，其中該TPU包含下列成分之反應產物：(1)一聚異氰酸酯成分，其包含、或基本上由、或係由六亞甲基-1,6-二異氰酸酯所組成；(2)如在此所描述之一多元醇成分；以及(3)一擴鏈劑成分，其包含、或基本上由、或係由以伸烷基取代之螺環化合物所組成，該螺環化合物包含以伸烷基取代的飽和螺環二醇、以伸烷基取代的飽和螺環-二胺、或其等之組合，其中該以伸烷基取代的螺環化合物，含有每個環具有5到7個原子的兩個環，且其中每個環被含有1至4個碳原子以羥基或胺封端的伸烷基所取代，其中該胺係為一級胺或二級胺，以增加一物件的抗化學性和耐玷污性。該用途還可以使得該物品更透明。 The technology of the present invention also includes the use of a thermoplastic polyurethane composition, wherein the TPU comprises the reaction product of the following components: (1) a polyisocyanate component comprising, or consisting essentially of, or consisting of hexamethylene (2) a polyol component as described herein; and (3) a chain extender component comprising, or consisting essentially of, or consisting of an alkylene The spiro compound is composed of a spiro compound substituted with an alkylene group, and the spiro compound includes a saturated spirocyclic diol substituted with an alkylene group, a saturated spirocyclic diamine substituted with an alkylene group, or a combination thereof, wherein the alkylene group A group-substituted spiro compound containing two rings each having 5 to 7 atoms, and wherein each ring is substituted by an alkylene group containing 1 to 4 carbon atoms terminated with a hydroxyl group or an amine, wherein the amine It is a primary or secondary amine to increase the chemical resistance and stain resistance of an object. This use can also make the item more transparent.
各種較佳特徵與具體實施例將通過以下之非限制性例示說明的方式來加以描述。 Various preferred features and embodiments will be described by way of non-limiting illustration below.
在此所描述的各化學成分之含量，係表示為不包括任何溶劑或稀釋油，其等一般係存在於商業材料中，也就是除非另有說明，在活性化學品的基礎下。然而，除非另有說明，否則在此所提及的每種化學品或組成物，應被解釋為商業級材料，其可以含有異構物、副產物、衍生物、以及通常可以被理解為商品級之其它此類物質。 The amounts of chemical constituents described herein are expressed exclusive of any solvents or diluent oils, which are generally present in commercial materials, that is, unless otherwise stated, on an active chemical basis. However, unless otherwise stated, every chemical or composition mentioned herein should be construed as a commercial grade material, which may contain isomers, by-products, derivatives, and generally understood as commercial other such substances.
無論是否有在上文中具體列出，上述所提及 之每個文獻均在此被併入以供參考，其等包括主張優先權之任何先前申請案。引述任何文件並不是承認該等文件，係在任何管轄區域可以作為先前技術，或是構成習於此藝者的一般知識。除了在具體實施例中或是有另外明確指出之外，本說明書中所指名之材料含量、反應條件、分子量、碳原子數等的所有數值均應理解為係以「大約」來修飾。應當理解的是，在此所說明之該等上限和下限、範圍與比例限制，係可以被獨立地組合。類似地，本發明的每種元素之範圍和含量，也可以與任何其他元素之範圍或含量一起運用。 Whether or not specifically listed above, the aforementioned Each of these documents, including any prior application to which priority is claimed, is hereby incorporated by reference. Citation of any document is not an admission that such document is prior art in any jurisdiction or constitutes the general knowledge of those skilled in the art. Except in specific examples or otherwise clearly stated, all numerical values such as material content, reaction conditions, molecular weight, carbon number, etc. specified in this specification should be understood as being modified by "approximately". It should be understood that the upper and lower limits, range and ratio limitations stated herein may be combined independently. Similarly, the ranges and amounts for each element of the invention can also be used with ranges or amounts for any other element.
在這些實施例中，該熱塑性聚胺甲酸酯係由表1中所列出的成分來合成。在表1中，SPG係指以伸烷基來取代之螺環化合物，其包括：
表1的TPU係依據ASTM D1003-11(使用BYK公司的Haze-gard Plus來進行測量)來測定霧狀程度、依據ASTM D6578M-13來測定永久性標記染色、並依據EN 438-2來測定抗化學性以進行評估以。在該永久性標記測試中，除了△E(使用Colorflex Hunterlab A60-1010-615比色計，來測量材料的顏色變化)係在5天後進行測量，而不是測試方法中所指定的24小時，同時期係採用以紅色溶劑為基礎的永久油墨標記，來取代該測試中所指定之以藍色溶劑為基礎的永久油墨標記以外，係依照ASTM D6578M-13來進行。該抗化學性結果係依據該測試方法所規定的標準，使用視覺評定等級0(破壞表面)至5(無損壞)來進行報告。測試結果係被總結於表2中。 The TPU in Table 1 is based on ASTM D1003-11 (measured using BYK Haze-gard Plus) to determine the degree of haze, according to ASTM D6578M-13 to determine permanent marker staining, and according to EN 438-2 to determine the resistance chemical properties to be evaluated. In this permanent marking test, except that △E (using a Colorflex Hunterlab A60-1010-615 colorimeter, to measure the color change of the material) is measured after 5 days instead of 24 hours as specified in the test method, At the same time, red solvent-based permanent ink marking was used to replace the blue solvent-based permanent ink marking specified in this test, which was carried out in accordance with ASTM D6578M-13. The chemical resistance results are reported using a visual rating scale of 0 (damaged surface) to 5 (no damage) according to the criteria specified in the test method. The test results are summarized in Table 2.
如上所示，依據本發明所製備的TPU組成物提供透明性，並具有防沾污性與抗化學性(如霧狀程度量測、永久性標記物測試、以及抗化學性降解測試所示)。 As shown above, the TPU composition prepared according to the present invention provides transparency, and has stain resistance and chemical resistance (as shown by haze degree measurement, permanent marker test, and chemical degradation resistance test) .
除非有另外說明，否則在此所提供之所有分子量值均為重量平均分子量。除非有另外說明，否則所有分子量數值均係通過GPC分析來確認。 All molecular weight values provided herein are weight average molecular weights unless otherwise stated. All molecular weight values were confirmed by GPC analysis unless otherwise stated.
如在此所使用的，與「包括」、「含有」或「特徵在於」同義的轉接詞「包含」，係為涵括性的或開放式的，並且不排除額外的、未被列舉的元素或方法步驟。然而，在此所提及的每個「包含」敘述中，該術語還意欲包括「基本上由......組成」以及「由......組成」之用語以作為替代具體實施例，其中「由...組成」係排除未指定的任何元素或步驟，而「基本上由......組成」 則允許包含額外之未列舉的元素或步驟，只要其等不會實質上影響所考量之組成物或方法之本質或基本的且新穎之特徵。 As used herein, the transition word "comprising", which is synonymous with "comprises", "comprises" or "characterized by", is inclusive or open-ended and does not exclude additional, non-recited element or method step. However, in every "comprising" statement mentioned herein, the term is also intended to include the phrases "consisting essentially of" and "consisting of" as an alternative to specific embodiment, wherein "consisting of" excludes any element or step not specified, and "consisting essentially of" It is permissible to include additional unlisted elements or steps as long as they do not materially affect the essence or basic and novel characteristics of the composition or method under consideration.
雖然某些代表性具體實施例與細節，已經基於例示說明本發明之目的來呈現，但是對於習於此藝來說，在不背離本發明之範圍的情況下，可以在其中進行各種改變和修改係為顯而易見的。就這一方面來說，本發明的範圍僅受限於以下隨附之申請專利範圍權利。 While certain representative embodiments and details have been presented for the purpose of illustrating the invention, various changes and modifications may be made therein by those skilled in the art without departing from the scope of the invention. is obvious. In this regard, the scope of the present invention is limited only by the claims in the appended claims below.
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